Azo dyestuffs containing alpha, alpha-bis(trifluoromethyl) benzyl alcohol groups



United States Patent 3,360,507 AZO DYESTUFFS CONTAINING u,a-BIS(TRIFLUO- ROMETHYL) BENZYL ALCOHOL GROUPS Willis A. Fisher, Snyder, and Russell I. Steiner, Williamsville, N.Y., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Dec. 3, 1964, Ser. No. 415,800 25 Claims. (Cl. 260-147) ABSTRACT OF THE DISCLOSURE Azo dyes, characterized in general by good fastness to washing, which correspond to the formula:

wherein Q is a residue of an azo dyestuif, n is a Whole number from 1 to 2 and Z is a substituent attached to an aromatic nucleus present in Q and Z corresponding to the structure OHF X: IIQ

wherein X X X and X, are halogens of atomic Weight 9 to 35 and s and t are integers 0 to 1. The azo dyes may contain, in addition to the above described group Z other substituents such as hydroxy, carboxy, sulfo, alkyl, alkoxy, sulfamyl and sulfonyl, for example. The dyes may also contain metallizable groups such as arylhydroxy and carboxy bound in positions adjacent to an azo bridge, which groups can be in complex combination with a metal of atomic weight 50 to 66, particularly copper or nickel. The dyes are prepared in known manner, i.e., by coupling a diazotizable amine and coupling component wherein either the amine or the coupling compound or both contains the group Z. The azo dyes are washfast and include watersoluble acid dyes for W001 and nylon, water-soluble direct dyes for Super polyamide and other synthetic fibers. The metalliferous water insoluble azo dyes produce strong, washfast color-ations on super polyamide fiber characterized by good fastness to light, dry cleaning, crocking and resistance to gas fading.

The present invention relates to novel azo dyestuffs. More particularly, it relates to novel azo dyestuffs which correspond to the structure wherein Q is the residue of an azo dyestutf, n is a whole number from 1 to 2 and Z is a substituent attached to an aromatic nucleus present in Q, said Z corresponding to the structure residue. In addition to the substituent Z described above,-

the residue Q may contain a variety of substituents for example sulfonic acid groups, carboxylic acid groups, sulfonic acid amide groups which may be N-monoor disubstituted; alkyl, alkoxy and sulfonyl (SO .)-alkyl groups particularly those containing up to 4 carbon atoms; aryl groups for example phenyl or naphthyl groups, nitro groups; and halogen atoms, e.g. fluorine, chlorine and bromine. The dyestuff may contain metallizable groups such as o,o'-dihydroxyazo, o-hydroxy-o'-carboxyazo, o-hydroxy-carboxy, e.g. salicyl groups, etc., which groups can be, if desired, in complex combination with a metal of atomic weight 50 to 66 particularly copper or nickel. The present novel structures include both water-insoluble and water-soluble dyestuffs, for example dyes rendered watersoluble by presence of one or more sulfonic acid substituents.

The mon-oand polyazo dyes of the invention are prepared in a manner well known to the azo dyestuif art by coupling a diazotizable amine with a coupling component wherein either the diazo compound or one coupling compound or both contains the aforementioned group Z. Suitable diazotizable amines containing Z can be prepared by the method described in US. patent application Ser. No. 329,889, assigned to this assignee. Suitable coupling components substituted with Z can be prepared in accordance with the methods disclosed in French Patent 1,325,- 204 and US. patent application Ser. No. 327,520, also assigned to this assignee.

Typical amines which can be employed in preparing the novel dyestuffs include:

p-amino-a,a-bis(trifluoromethyl)benzyl alcohol 2-amino-4-nitrobenzenesulfonic acid sulfanilic acid metanilic acid 4-aminonaphthalene sulfonic acid 3-amino-1,S-naphthalenedisulfonic acid 6-amino-1,3-naphthalenedisulfonic acid p-toluidine 4amino-3,5-dimethyl-a,a-bis (chlorodifluoromethyl) benzyl alcohol p-amino-a,u-bis (chlorodifluoromethyl) benzyl alcohol 4-amino-2-chloro-a -bis (trifluoromethyl) benzyl alcohol p-aminophenol o-aminophenol 4-nitro-2-aminophe-nol Z-ethoxyaniline aniline Coupling components which can be used for preparing the novel dyes of invention include the following representative examples:

2-naphth0l-3,6-disulfonic acid 1hydroxy-a,u-bis trifiuoromethyl) -2-naphthalenemethanol 1,5-dihydroxy-u,a,a',a'-tetrakis trifluoromethyl -2,6- naphthalenedimethanol 1,5-dlhYdI'OXY-Ot,0t,0t',Ot'-ttfakiS (chlorodifluoromethyl 2,6-naphthalenedimethanol l,5-dibydroxy-a,a-bis chloroditluoromethyl -2- naphthalenemethanol 6,6'-ureylene bis l-naphthol-S-sulfonic acid) 2-hydroxy-a,a-bis (chlorodifiuoromethyl benzyl alcohol acetoacetanilide 5 -pyrazolone phenol 3-methyl-5-pyrazolone 1-phenyl-3-methyl-5-pyrazolone 1- 2-chl0rophenyl) -3-methyl-5-pyrazolone 1-.( 3 -nitrophenyl) -3 -methyl-5 -pyrazolonc 1- (3 -sulfamylphenyl -3 -methyl-5-pyrazolone p-cresol resorcinol B-naphthol 5-chlor-o-l-napl1thol p-chlorophenol 2,4-dihydroxy-u,a-bis trifluoromethyl benzyl alcohol Metalliferous dyestuffs contemplated by the present invention can be readily prepared by treating umnetallized dyes of the invention containing metallizable groups by known methods with an agent yielding a metal of atomic weight 50 to 66, and particularly copper or nickel, e.g. an acetate, sulfate, acetylacetonate, formate, or like salt of the .metal, in the presence of an organic solvent, for

example diethylene glycol, dimethyl formamide, glycerine, ethoxyethanol (Cellosolve) and the monoethyl ether of diethylene glycol Carbitol). Conveniently, metallization is carried out using a metal acetate in dimethyl formarnide.

The novel water soluble dyestuffs of this invention include direct dyes for coloring cotton as well as acid dyes for coloring wool and nylon according to conventional dyeing techniques.

Metallized as well as unmetallized water-insoluble dyes of the invention can be used todye synthetic hydrophobic fibers e.g. superpolyamide fiber, Dacron, cellulose acetate and the like according to the well known disperse dyeing techniques wherein the color is applied to the fiber from aqueous dispersions obtained with the aid of dispersing agents, e.g. sodium lignosulfonate, waste sulfate liquor, a formaldehyde condensation product of an .alkyl naphthalene sulfonate, or a formaldehyde condensation product of a naphthalene B-sulfonate.

Water-insoluble metalliferous monoazo dyes of the invention constitute a particularly valuable class of dyes which color superpolyamide fibers e.g. poly e-caprolactam (Nylon 6), polyhexamethylene adiparnide (Nylon 6,6), polyundecamide (Nylon 11) and polyhexamethylene sebacamide (Nylon 610) from aqueous dye baths in heavy shades which possess good wash fastness, excellent levelness, fastness to light, dry cleaning, and crocking, and resistance to gas fading.

The following examples illustrate the preparation and application of the novel dyes of the invention but it is to be understood that the invention is not to be limited by the specific details of these examples, since, as will be obvious to those skilled in the art, changes can be made in these details without departing from the scope or spirit of the invention. The temperatures are in degrees centigrade and parts and percentages are by weight.

EXAMPLE 1 A. Coupling A solution of 50.6 parts (0.175 mol) of 4-amino-3- rnethoxy-a-,a-bis(trifluoromethyl) benzyl alcohol prepared as described in US. patent application Serial No. 329,889, in a mixture of 52.5 parts water and 51 parts 20 B. hydrochloric acid was cooled to about Over a period of about minutes a 4 N aqueous solution con taining 12.6 parts (0.175 mol) sodium nitrite was added to the mixture which was maintained at a temperature of 05 during the addition. On completion of the addition, the mass was agitated for 30 minutes at 05. The resulting diazonium salt solution was added over& period of about 45 minutes to 21 parts (0.194 mol) of p-cresol dissolved in a mixture of 350 parts of water, 139 parts 50 B. sodium hydroxide and 52.5 parts of sodium carbonate. The coupling mass Was heated to 40 and filtered. The filter cake was washed free of alkali and inorganic salts with 4000 parts of water and dried in air at '75. The yield of a,a-bis(trifiuoromethyl)-3-methoxy-4-(2-hydroxy-5-methylphenylazo) benzyl alcohol was 68.5 parts (0.168 mol 9 6% of theory).

B. Metallation 0 H O H (I? F a l l HOCC N=N Cu complex I (1 1) C F:

was sand ground with 37 parts of formaldehyde-naphthalene p-sulfonic acid condensation product (Tarnol N) and 37 parts of lignin sulfonate (Marasperse N) and spray dried. The resulting dyestuff composition dispersed in water, dyed Nylon 6 and Nylon 6,6 in attractive bluishred shades of excellent levelness, fastness to light, washing, crocking and dry cleaning and resistance to gas fading.

EXAMPLE 2 In a manner according to that described in Example 1, Part A, 13.8 parts (0.05 mol) of 4-amino-3-hydroxy-a,abis(trifluoromethyl) benzyl alcohol was diazotized in aqueous medium and coupled into 20.8 parts (0.082 mol) of 1-(3-sulfamylphenyl)-3-methylpyrazolone to obtain 22.4 parts (83% of theory) of the dyestufi S OaNH:

The above dye dispersed in water provided level bright yellow colorations on cellulose acetate.

The 1:1 copper complex of the above dye prepared in accordance with method of Example 1, Part B, dyed Nylon 6,6 and Nylon 6, yellow-brown shades of excellent levelness and fastness to light, washing and dry cleaning.

EXAMPLES 3-4 In the following examples set forth in Table I, unmetallized monoazo dyestuffs were prepared from the amines and coupling components listed by a method according to that described in Example 1, Part A. The

corresponding metal derivatives of the dyestuffs were prepared in accordance with the procedure of Example 1, Part B.

TABn-is I Shade of Dyeing Metallized Shade of Dyeing of Example Amine Coupling Component of Unifietallized Dye Metallized Dye 3 4-nitro-o-anisidine 2,4-dihydrxy-a,a-bis(tri- Cu (1:1) Violet on Nylon 6 and fiuoromethyDbenzyl Nylon 6,6. alcohol.

4 4-811111'10 3-hYdf0XY-a,a blS fi-naphthol Orange on Cu (1:1) Blulsh red on Nylon (tnfluoromethyl) benzyl Dacron. 6 and Nylon 6,6. alcohol.

EXAMPLE 5 fiuoromethyl) benzyl alcohol was diazotized in aqueous The following example illustrated the dyeing of Nylon 6,6 and Nylon 6 with the metallized dyestuff of Example 1.

About 0.5 part of the copper containing dye of Example 1 was pasted with 1 part of a 10% aqueous solution of an alkyl polyether alcohol (Triton X-67) and the remedium. Over a period of 30 minutes the aqueous diazomum salt was added to an agitated mixture of 19.1 parts (0.055 part) of 2-naphtho-l-3,6-disulfonic acid, disodium salt, 397 parts of 50% aqueous sodium hydroxide, 15 parts sodium carbonate and 300 parts of water maintained at a temperature of 05. Upon the completion of the addition the coupling mass was agitated for 15 minutes sulting mixture was diluted with suflicient water at 9 0 0 at 0-5 and heated to 80". Sodium chloride (60 parts) to provide 500 parts of aqueous dispersion.

Nylon 6,6 tricot (10 parts) was immersed for 20 minutes in a bath at containing 344 parts of water, 2 parts of a 10% aqueous solution of a sodium sulfate of a fatty acid ester (Tetranol) and 4 parts of a 10% aqueous solution of ammonium sulfate. The fiber was withdrawn and parts of the aqueous dye dispersion were charged. The fiber was immersed in the dye bath for 20 minutes at 40 with frequent agitation. Over a period of 45 minutes the bath was heated to 95 and maintained at that temperature for 45 minutes. The goods were withdrawn, rinsed with water at ambient temperature and dried. A 10 part sample of Nylon 6, tricot was dyed in like manner. The Nylon 6,6 and 'Nylon 6 samples were dyed in attractive bluish-red shades characterized by excellent levelness, fastness to light, Wet processing and crocking as well as high resistance to gas fading. The dyeings obtained were superior in build-up of color and 'fastness to light, washing and crocking, tosimilar dycings obtained on Nylon 6,6 and Nylon 6 using the copper complex of the product obtained by coupling o-anisidine into p-cresol.

EXAMPLE 6 In a manner analogous to that described in Example 1, Part A, 0.13 part (0.05 mol) of 4-amino-a,u-bis(triwas added and the mixture was cooled to 4045. The precipitated orange solid was recovered by filtration, washed with 53.5 parts of 10% aqueous sodium chloride and dried at The product corresponding to the struc- 30 ture OH some (13F: l HOC\N.=N

| soon;

was obtained in excellent yield, and dyes wool and nylon from an acid bath in bright heavy orange shades, characterized by excellent fastness to light and Washing.

EXAMPLES 7-17 In the following examples presented in Table II monazo acid dyestuffs were prepared from the amines and coupling components listed according to the method described in Example 6.

TABLE II Example Amine Coupling Componentj Shade of Dyeing Wool Dyeing Z-amino 5-nitrobenl-hydroxy-a,a-bis (trifluoromctliyl)'--' Brown from sulfuric acid bath; zene sulfonic acid. 2-naphthalene-methanol. violet from. acetic acid bath. Sulfanilic acid .do Scarlet-orange. Naphthiom'c acid .do Red. Sulianilic acid 1,5-dihydl'OXy-oz,a,a',a-tetlt Bordeaux.

fluoromethyl)-2,6naphthalene dimethanol. kaminonaphthalene do Violet.

sulfonic acid. s-amino-Lfi-naphtha- Same as Example 7 Orange-red.

lene disulfonic acid. 5-amino-1,3-naphtha- -do Do lene disulfonic acid. 7 3-ann'no-Lonaphtha- Same as Example 10 Violet.

lena disulfonie acid. 6-amino-1,3-naphthado Do.

lene disulfonic acid. Metanilic acid 1, 5-dihydroxy-a,a,a,a-tetrakis Deep bordeaux red.

(chlorodifiuoromethyD-2, 6naphthalenedimethanol. 17 .do 1, 5-dihydroxy-a,a,-bis(chloro- Do.

difluoromethyl)-2-naphthalenemethanol.

7 EXAMPLES 18-20 In the following examples set forth in Table III waterinsoluble, non-metallized monoazodyestufis were prepared from the amines and coupling components listed, according to the procedure described in Example 1, Part A. These disperse dyes colored the synthetic fibers listed in the table in attractive shades, of good fastness to light and washing.

TABLE III Ex. Amino Coupling Shade of Component Dyeing 18-.-- 4-8mlI10-a,a-blS (trlfluorc- Phenol Yellow on methyl) benzyl alcohol). cellulose. 19..-- p-toluidine Same as Ex- Bordeaux ample 16. on nylon. 20--.- do Same as Ex- Deep red on ample 17. nylon.

EXAMPLE 21 According to the proceduredescribed in Example 6, 13 parts (0.05 mol) of 4-amino-a,a-bis(trifiuoromet-hyl) benzyl alcohol were diazotized and coupled into 13.8 parts (0.027 mol) of 6,6'-ureylenebis-l-naphthol-3-sulfonicacid in aqueous medium to obtain an excellent yield of the disazo dye corresponding to the structure which dyed cotton in orange shades.

EXAMPLE 22 By a procedure according to that described in Example 21, 4,4'-diamino-2,7-stilbene disulfonic acid was diazotized andcoupled with two molar equivalents of 2-hydroxy-a,a-bis(chlorodifiuoromethyl)benzyl alcohol to produce a good yield of a yellow dye for cotton.

We claim:

1. An azo dyestuff of the structure wherein Q is a residue of an azo dyestuff containing at least one aromatic residue which may contain one or more substituents selected from the group consisting of sulfonic acid, carboxylic acid, sulfonic acid amide, alkyl, alkoxy, sulfonyl alkyl, aryl, nitro and hydroxy or a halogen atom which may be fluorine, chlorine or bromine, n is a whole number from 1 to 2 and Z is a substituent directly attached to a carbon atom of an aromatic nucleus present in Q, said Z corresponding to the structure wherein X X X and X, are each fluorine, chlorine or bromine, and s and t are integers 0 to 1.

2. A metal complex derivative of an azo dye having the structural formula wherein M is a metal having an atomic weight between 50 and 66, Q is the residue of an azo dyestufi as defined in claim 1 and containing a metallizable group, and (Z) is as in claim 1.

0 CH3 0 CH3 (FF; l

CFa l SO H S OH

CIFzC-C-CFaCl ClFaC- G FaCl OH I (FF:

Hoes- O NEE-(J-NH- 80:11

21. A copper complex derivative of an azo dye having the structural formula OH OH OF: I 1

22. A copper complex derivative of an azo dye having the structural formula N Cu SOzNHa 23. A copper complex derivative of an azo dye having the structural formula 0 CH3 OH Cu C(OH 24. A copper complex derivative of an azo dye having the structural formula 25. The azodyestuflf obtained by coupling diazotized metanilic acid into 1,5-dihydroxy a,a-bis(chlorodifluoromethyl)2-naphthalene methanol.

References Cited UNITED STATES PATENTS 2,700,686 1/ 1955 Dickey et al. 260196 X FLOYD D. HIGEL, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,360,507 December 26, 1967 Willis A. Fisher et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Columns 5 and 6, Table II, second column, opposite Example 12 for "s-amino-l ,5-" read S-amino-l ,5- column 7, lines 70 to 75, the formula should appear as shown below instead of as in the patent:

OCH H H0 C N=N column 8, claim 5, the formula should appear as shown below instead of as in the patent:

OCH OH 0 =N OH same column 8, claim 11, the formula should appear as shown below instead of as in the patent:

on F CC---CF 3 3 HO S-ON=N OH columns 10 and 11, claim 20, the formula should appear as shown below instead of as in the atent:

Signed and sealed this 22nd day of April 1969.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Cbmmissioner of Patents 

1. AN AZO DYESTUFF OF THE STRUCTURE 